N-alkoxy-4,4-dioxy-polyalkyl-piperidines as radical polymerization inhibitors

ABSTRACT

The present invention relates to selected glycidyl or carbonyl functional N-alkoxy-4,4-dioxy-polyalkyl-piperidine compounds forming an open chain or cyclic ketal structure, a polymerizable composition comprising a) at least one ethylenically unsaturated monomer and b) a glycidyl or carbonyl functional N-alkoxy-4,4-dioxy-polyalkyl-piperidine nitroxide initiator compound. Further aspects of the present invention are a process for polymerizing ethylenically unsaturated monomers and the use of glycidyl or carbonyl functional N-alkoxy-4,4-dioxy-polyalkyl-piperidine nitroxide initiators for radical polymerization.

The present invention relates to selected glycidyl or carbonylfunctional N-alkoxy-4,4-dioxy-polyalkyl-piperidine compounds forming anopen chain or cyclic ketal structure, a polymerizable compositioncomprising a) at least one ethylenically unsaturated monomer and b) aglycidyl or carbonyl functional N-alkoxy-4,4-dioxy-polyalkyl-piperidinenitroxide initiator compound. Further aspects of the present inventionare a process for polymerizing ethylenically unsaturated monomers andthe use of glycidyl or carbonyl functionalN-alkoxy-4,4-dioxy-polyalkyl-piperidine nitroxide initiators for radicalpolymerization.

The compounds of the present invention provide polymeric resin productshaving low polydispersity and the polymerization process proceeds withgood monomer to polymer conversion efficiency. In particular, thisinvention relates to stable free radical-mediated polymerizationprocesses which provide homopolymers, random copolymers, blockcopolymers, multiblock copolymers, graft copolymers and the like, atenhanced rates of polymerization and enhanced monomer to polymerconversions.

U.S. Pat. No. 4,581,429 to Solomon et al., issued Apr. 8, 1986,discloses a free radical polymerization process which controls thegrowth of polymer chains to produce short chain or oligomerichomopolymers and copolymers, including block and graft copolymers. Theprocess employs an initiator having the formula (in part) R′R″N—O—X,where X is a free radical species capable of polymerizing unsaturatedmonomers. The reactions typically have low conversion rates.Specifically mentioned radical R′R″N—O. groups are derived from 1,1,3,3tetraethylisoindoline, 1,1,3,3 tetrapropylisoindoline, 2,2,6,6tetramethylpiperidine, 2,2,5,5 tetramethylpyrrolidine ordi-t-butylamine. However, the suggested compounds do not fulfill allrequirements. Particularly the polymerization of acrylates does notproceed fast enough and/or the monomer to polymer conversion is not ashigh as desired.

The radical initiators, polymerization processes and resin products ofthe present invention have an additional glycidyl or carbonyl group,which can be used for further reactions. The resulting resins are usefulin many applications.

The glycidyl or alkylcarbonyl group of the present initiators remainsessentially unchanged during the radical polymerization reaction.Therefore the radical initiators of the present invention offer thepossibility, after the radical polymerization is accomplished orstopped, to react the glycidyl group of the oligomers or polymers in asecond step with nucleophiles such as alcohols, mercaptanes, amines,metal organic compounds or the like, thereby changing the properties ofthe oligomers or polymers.

The glycidyl group of the initiators can also be reacted in a first stepfor example by anionic polymerization in the presence of for exampledicyandiamide, butyl-Lithium or other strong bases leading tooligomeric/polymeric radical initiators.

S. Kobatake et al, Macromolecules 1997, 30, 42384242 and in WO 97136894disclose the anionic polymerization of butadiene in the presence ofcompound (a) which contains a glycidyl group in a side chain. Thiscompound acts as a terminating reagent for the anionic polymerization ofbutadiene.

The resulting macromolecule can be further used as a macroinitiator forradical polymerization and for preparing block copolymers containing apoylbutadiene segment. Typical copolymers which can be produced areacrylnitrile/butadiene/styrene (ABS) copolymers.

The present invention provides initiators for radical polymerizationwhich contain the glycidyl or alkylcarbonyl group attached to the phenylgroup. The initiators show a high reactivity, good rates ofpolymerization and good monomer to polymer conversions.

The remaining glycidyl or carbonyl group is highly reactive towardsnucleophiles and can readily be transformed into other chemical groupsif desired.

The compounds of the present invention are also useful as terminatingagents in the anionic polymerization of for example butadiene asdescribed in WO 97/36894. With the instant compounds termination ofanionic polymerization of for example butadiene proceeds fast andcomplete.

Glycidyl or carbonyl functional alkoxyamines containing atetramethyl-piperidine group and their use as functionalized radicalinitiators/regulators have already been described in WO 99/46261. Theinstant compounds differ from those disclosed in WO 99/46261 in thatthey have a ketal structure in 4 position of the piperidine moiety. Suchcompounds and their use as polymerization initiators/regulators haveneither been disclosed as specific compounds nor generically in theprior art.

It has now been found, that amongst those 2,2,6,6-tetraalkylpiperidinesdescribed in the prior art those are of particular value which arederivatives of 2,2,6,6 tetramethyl piperidine, 2,2 diethyl-6,6 dimethylpiperidine and of 2,6-diethyl-2,3,6-trimethyl piperidine which aresubstituted in the 4 position by two oxygen atoms forming an open chainor cyclic ketal structure.

The ketal structure in 4 position ensures high thermal stability whichis important for storage, particularly at elevated temperatures. Theketal structure is thermally significantly more stable compared to thecorresponding 4-oxo compound.

The compounds exhibit an unchanged initiating/regulating activity evenafter storage at elevated temperatures as for example used inconventional stability tests.

Another problem associated with nitroxyl or nitroxyl ether mediated freeradical polymerization is the formation of a significant color of theresulting polymer. The compounds of the present invention which have aketal structure in 4-position impart less color to the polymer comparedto other prior art compounds of similar structure.

The steric hindrance introduced by the two di thyl groups instead of twomethyl groups further leads to an optimized balance in terms ofstability of the compounds, initiating activity and control ofpolymerization.

The particular substitution pattern in 2 and 6 position of thepiperidine ring allows high monomer to polymer conversions in shorttimes and low polydispersities which are generally below 2. High monomerto polymer conversions are even achieved with acrylates, such as ethyl-or butyl-acrylate. The temperature necessary to achieve high conversionin short times may be for example as low as 120° C.

The present invention provides compounds useful as initiators/regulatorsfor controlled radical polymerization which in addition have a highlyreactive functional group allowing polymer analogous reactions oranionic polymerization termination, which can be adjusted in theirinitiating/controlling efficiency by adjusting the steric hindrance atthe nitrogen atom and which have an excellent storage stability andimpart none or only little color to the final polymer.

The compounds of the present invention are novel and consequently onesubject of the instant invention is a compound of formula Ia, IIa orIIIa

wherein

D is a group

or a group C(O)—R₁₃;

R₁₃ is phenyl or C₁–C₁₈alkyl;

m is 1, 2 or 3;

n is 1 or 2;

if n is 1

Y and Y′ are independently C₁–C₁₂alkyl, C₃–C₁₂alkenyl, C₃–C₁₂alkinyl,C₅–C₈cycloalkyl, phenyl, naphthyl, C₇–C₉phenylalkyl; or

Y and Y′ together form one of the bivalent groups —C(R₁)(R₂)—CH(R₃)—,CH(R₁)—CH₂—C(R₂)(R₃)—, —CH(R₂)—CH₂—C(R₁)(R₃)—, —CH₂—C(R₁)(R₂)—CH(R₃)—,o-phenylene, 1,2-cyclohexyliden,

—CH₂—CH═CH—CH₂— or

wherein

R₁ is hydrogen, C₁–C₁₂alkyl, COOH, COO—(C₁–C₁₂)alkyl or CH₂OR₄;

R₂ and R₃ are independently hydrogen, methyl ethyl, COOH orCOO—(C₁–C₁₂)alkyl;

R₄ is hydrogen, C₁–C₁₂alkyl, benzyl, or a monovalent acyl residuederived from an aliphatic, cycloaliphatic or aromatic monocarboxylicacid having up to 18 carbon atoms;

if n is 2

Y and Y′ together form one of the tetravalent groups

wherein

Q is a bisacyl residue which is derived from a C₂–C₁₂dicarboxylic acidor C₁–C₁₂alkylene;

Z is C₁–C₁₂alkylene; the R₁₂ are independently of each other H or CH₃.

C₁–C₁₈alkyl can be linear or branched. Examples are methyl, ethyl,propyl, isopropyl, butyl, 2-butyl, isobutyl, t-butyl, pentyl, 2-pentyl,hexyl, heptyl, octyl, 2-ethylhexyl, t-octyl, nonyl, decyl, undecyl,dodecyl, heptadecyl or octadecyl.

Alkenyl having from 3 to 12 carbon atoms is a branched or unbranchedradical, for example propenyl, 2-butenyl, 3-butenyl, isobutenyl,n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl,isododecenyl.

Alkinyl having from 3 to 12 carbon atoms is a branched or unbranchedradical, for example propinyl (—CH₂—C≡CH), 2-butinyl, 3-butinyl,n-2-octinyl or n-2-dodecinyl.

Examples of alkoxy are methoxy, ethoxy, propoxy, isopropoxy, butoxy,isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy or octoxy.

C₇–C₉phenylalkyl is for example benzyl, α-methylbenzyl,α,α-dimethylbenzyl or 2-phenylethyl, benzyl is preferred.

C₁–C₁₂alkylene is a branched or unbranched radical, for examplemethylene, ethylene, propylene, trimethylene, tetramethylene,pentamethylene, hexamethylene, heptamethylene, octamethylene,decamethylene or dodecamethylene.

C₅–C₈cycloalkyl is for example cyclopentyl, cyclohexyl, cycloheptyl,methylcyclopentyl or cyclooctyl.

Examples of a monocarboxylic acid having up to 18 carbon atoms areformic acid, acetic acid, propionic acid, the isomers of valeric acid,methyl ethyl acetic acid, trimethyl acetic acid, capronic acid, lauricacid or stearic acid. Examples for unsaturated aliphatic acids areacrylic acid, m thacrylic acid, crotonic acid, linolic acid and oleicacid.

Typical examples of cycloaliphatic carboxylic acids are cyclohexanecarboxylic acid or cyclopentane carboxylic acid.

Examples of aromatic carboxylic acids are benzoic acid, salicylic acidor cinnamic acid.

Examples of dicarboxylic acids are oxalic acid, malonic acid, succinicacid, glutaric acid, adipic acid, sebatic acid, fumaric acid, maleicacid, phthalic acid, isophthalic acid, terephthalic acid.

Preferred is a compound wherein in the formulae Ia, IIa or IIIa D is agroup

Particularly preferred is a compound of formula Ia, IIa or IIIa wherein

D is a group

m is 1;

n is 1;

Y and Y′ are independently C₁–C₁₂alkyl, C₃–C₁₂alkenyl, phenyl or benzyl;or

Y and Y′ together form one of the bivalent groups —C(R₁)(R₂)—CH(R₃)—,CH(R₁)—CH₂—C(R₂)(R₃)—, —CH(R₂)—CH₂—C(R₁)(R₃)—, —CH₂—C(R₁)(R₂)—CH(R₃)—,—CH₂—CH═CH—CH₂— or

wherein

R₁ is hydrogen, C₁–C₁₂alkyl, COO—(C₁–C₁₂)alkyl or CH₂OR₄;

R₂ and R₃ are independently hydrogen, methyl ethyl, orCOO—(C₁–C₁₂)alkyl;

R₄ is hydrogen, C₁–C₁₂alkyl, benzyl, or a monovalent acyl residuederived from an aliphatic, cycloaliphatic or aromatic monocarboxylicacid having up to 12 carbon atoms and one of the R₁₂ is hydrogen and theother is methyl.

More preferred is a compound of formula Ia, IIa or IIIa wherein

D is a group

m is 1;

n is 1;

Y and Y′ together form one of the bivalent groups —CH₂—C(R₁)(R₂)—CH(R₃)—wherein

R₁ is hydrogen, methyl or ethyl;

R₂ and R₃ are independently hydrogen, methyl ethyl, orCOO—(C₁–C₁₂)alkyl; and

one of the R₁₂ is hydrogen and the other is methyl.

Especially preferred is a compound of formula IIIa.

Specifically preferred compounds are listed in Tables 1, 2 and 3.

TABLE 1 1.)2,6-Diethyl-4,4-dimethoxy-2,3,6-trimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

2.)4,4-Diethoxy-2,6-diethyl-2,3,6-trimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

3.)2,6-Diethyl-2,3,6-trimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-4,4-dipropoxy-piperidine

4.)4,4-Dibutoxy-2,6-diethyl-2,3,6-trimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

5.)2,6-Diethyl-4,4-diisobutoxy-2,3,6-trimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

6.)2,6-Diethyl-2,3,6-trimethyl-4,4-bis-octyloxy-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

7.)4,4-Bis-allyloxy-2,6-diethyl-2,3,6-trimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

8.)4,4-Bis-cyclohexyloxy-2,6-diethyl-2,3,6-trimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

9.)4,4-Bis-benzyloxy-2,6-diethyl-2,3,6-trimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

10.)7,9-Diethyl-6,7,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

11.)7,9-Diethyl-2,6,7,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

12.)2,7,9-Triethyl-6,7,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

13.)7,9-Diethyl-6,7,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-2-propyl-1,4-dioxa-8-aza-spiro[4.5]decane

14.)2-Butyl-7,9-diethyl-6,7,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

15.)7,9-Diethyl-6,7,9-trimethyl-2-octyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

16.)2-Decyl-7,9-diethyl-6,7,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

17.)2-Dodecyl-7,9-diethyl-6,7,9-trimethyl-8-[1-(4-oxiranylmethoxy)-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

18.){7,9-Diethyl-6,7,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]dec-2-yl}-methanol

19.) Acetic acid 7,9-diethyl-6,7,9-trim thyl-8-[1-(4-oxiranylmthoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]dec-2-ylmethyl ester

20.) Octadecanoic acid7,9-diethyl-6,7,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4,5]dec-2-ylmethylester

21.) Benzoic acid7,9-diethyl-6,7,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]dec-2-ylmethylester

22.)7,9-Diethyl-2-methoxymethyl-6,7,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

23.)2-Cyclohexyloxymethyl-7,9-diethyl-6,7,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

24.)2-Benzyloxymethyl-7,9-diethyl-6,7,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

25.) Octanedioic acidbis-{7,9-diethyl-6,7,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]dec-2-ylmethyl}ester

26.) Terephthalic acidbis-{7,9-diethyl-6,7,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]dec-2-ylmethyl}ester

27.)1′,4′-Bis-{7,9-diethyl-6,7,9-trimethyl-8-(1-(4-oxiranylmethoxy-phenyl)-ethoxy)-1,4-dioxa-8-aza-spiro[4.5]dec-2-ylmethyl}-oxybutane

28.)7,9-Diethyl-2,2,6,7,9-pentamethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

29.)7,9-Diethyl-2,3,6,7,9-pentamethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

30.)4,4-(o-Phenylendioxy)-2,6-diethyl-2,3,6-trimethyl-1-[1′-(4′-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

31.)4,4-(1′,2′-cyclohexylendioxy)-2,6-diethyl-2,3,6-trimethyl-1-[1″-(4″-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

32.)7,9-Diethyl-6,7,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane-2,3-dicarboxylicacid dimethyl ester

33.) 8,10-Diethyl-7,8,10-trimthyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

34.)8,10-Diethyl-3,3,7,8,10-pentamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

35.)3,8,10-Triethyl-3,7,8,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

36.)3,3,8,10-Tetraethyl-7,8,10-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

37.)8,10-Diethyl-3,7,8,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-3-propyl-1,5-dioxa-9-aza-spiro[5.5]undecane

38.)3-Butyl-3,8,10-triethyl-7,8,10-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

39.)2,4-Diethyl-1,2,4-trimethyl-3-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-7,16-dioxa-3-aza-dispiro[5.2.5.2]hexadec-11-ene

40.){8,10-Diethyl-3,7,8,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undec-3-yl}-methanol

41.){3,8,10-Triethyl-7,8,10-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undec-3-yl}-methanol

42.)8,10-Diethyl-3-methoxymethyl-3,7,8,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

43.)3-Cyclohexyloxymethyl-8,10-diethyl-3,7,8,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

44.)3-Benzyloxymethyl-8,10-diethyl-3,7,8,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

45.) Acetic acid8,10-diethyl-3,7,8,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undec-3-ylmethylester

46.) Octanedioic acidbis-{8,10-diethyl-3,7,8,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undec-3-ylmethyl}ester

47.)1′,6′-Bis-{3,8,10-triethyl-7,8,10-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undec-3-ylmethyl}-oxyhexane

48.)8,10-Diethyl-3,7,8,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane-3-carboxylicacid methyl ester

49.)8,10-Diethyl-7,8,10-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane-3,3-dicarboxylicacid diethyl ester

50.)3,3-Bis-{8,10-diethyl-7,8,10-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza}-spiro[5.5]undecane

51.)2,4-Diethyl-1,2,4-trimethyl-3-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-7,12-dioxa-3-aza-spiro[5.6]dodec-9-ene

TABLE 2 1.)2,2-Diethyl-4,4-dimethoxy-6,6-dimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

2.)4,4-Diethoxy-2,2-diethyl-6,6-dimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

3.)2,2-Diethyl-6,6-dimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-4,4-dipropoxy-piperidine

4.)4,4-Dibutoxy-2,2-diethyl-6,6-dimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

5.)2,2-Diethyl-4,4-diisobutoxy-6,6-dimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

6.)2,2-Diethyl-6,6-dimethyl-4,4-bis-octyloxy-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

7.)4,4-Bis-allyloxy-2,2-diethyl-6,6-dimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

8.)4,4-Bis-cyclohexyloxy-2,2-diethyl-6,6-dimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

9.)4,4-Bis-benzyloxy-2,2-diethyl-6,6-dimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

10.) 7,7-Diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-thoxy]-1,4-dioxa-8-aza-spiro[4.5]d cane

11.)7,7-Diethyl-2,9,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

12.)2,7,7-Triethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

13.)7,7-Diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-2-propyl-1,4-dioxa-8-aza-spiro[4.5]decane

14.)2-Butyl-7,7-diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

15.)7,7-Diethyl-9,9-dimethyl-2-octyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

16.)2-Decyl-7,7-diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

17.)2-Dodecyl-7,7-diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

18.){7,7-Diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]dec-2-yl}-methanol

19.) Acetic acid7,7-diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]dec-2-ylmethylester

20.) Octadecanoic acid7,7-diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]dec-2-ylmethylester

21.) Benzoic acid7,7-diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]dec-2-ylmethylester

22.)7,7-Diethyl-2-methoxymethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

23.)2-Cyclohexyloxymethyl-7,7-diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

24.)2-Benzyloxymethyl-7,7-diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

25.) Octanedioic acidbis-[7,7-diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]dec-2-ylmethyl}ester

26.) Terephthalic acidbis-{7,7-diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]dec-2-ylmethyl}ester

27.)1′,4′-Bis-{7,7-diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]dec-2-ylmethyl}-oxybutane

28.)7,7-Diethyl-2,2,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

29.)7,7-Diethyl-2,3,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

30.)4,4-(o-Phenylendioxy)-2,2-diethyl-6,6-dimethyl-1-[1′-(4′-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

31.)4,4-(1′,2′-cyclohexylendioxy)-2,2-diethyl-6,6-dimethyl-1-[1″-(4″-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

32.)7,7-Diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane-2,3-dicarboxylicacid dimethyl ester

33.)8,8-Diethyl-10,10-dimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

34.)8,8-Diethyl-3,3,10,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

35.)3,8,8-Triethyl-3,10,10-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

36.)3,3,8,8-Tetraethyl-10,10-dimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

37.)8,8-Diethyl-3,10,10-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-3-propyl-1,5-dioxa-9-aza-spiro[5.5]undecane

38.)3-Butyl-3,8,8-triethyl-10,10-dimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

39.)2,2-Diethyl-4,4-dimethyl-3-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-7,16-dioxa-3-aza-dispiro[5.2.5.2]hexadec-11-ene

40.){8,8-Diethyl-3,10,10-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undec-3-yl}-methanol

41.){3,8,8-Triethyl-10,10-dimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undec-3-yl}-methanol

42.)8,8-Diethyl-3-methoxymethyl-3,10,10-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

43.)3-Cyclohexyloxymethyl-8,8-diethyl-3,10,10-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

44.)3-Benzyloxymethyl-8,8-diethyl-3,10,10-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

45.) Acetic acid8,8-diethyl-3,10,10-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undec-3-ylmethylester

46.) Octanedioic acidbis-{8,8-diethyl-3,10,10-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undec-3-ylmethyl}ester

47.)1′,6′-Bis-{3,8,8-triethyl-10,10-dimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undec-3-ylmethyl}-oxyhexane

48.)8,8-Diethyl-3,10,10-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane-3-carboxylicacid methyl ester

49.)8,8-Diethyl-10,10-dimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane-3,3-dicarboxylicacid diethyl ester

50.)3,3-Bis-{8,8-diethyl-10,10-dimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza}-spiro[5.5]undecane

51.)2,2-Diethyl-4,4-dimethyl-3-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-7,12-dioxa-3-aza-spiro[5.6]dodec-9-ene

TABLE 3 1.)4,4-Dimethoxy-2,2,6,6-tetramethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

2.)4,4-Diethoxy-2,2,6,6-tetramethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]piperidine

3.)2,2,6,6-Tetramethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-4,4-dipropoxy-piperidine

4.)4,4-Dibutoxy-2,2,6,6-tetramethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

5.)4,4-Diisobutoxy-2,2,6,6-tetramethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

6.)2,2,6,6-Tetramethyl-4,4-bis-octyloxy-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

7.)4,4-Bis-allyloxy-2,2,6,6-tetramethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

8.)4,4-Bis-cyclohexyloxy-2,2,6,6-tetramethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

9.)4,4-Bis-benzyloxy-2,2,6,6-tetramethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

10.)7,7,9,9-Tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

11.)2,7,7,9,9-Pentamethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

12.)2-Ethyl-7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

13.)7,7,9,9-Tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-2-propyl-1,4-dioxa-8-aza-spiro[4.5]decane

14.)2-Butyl-7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

15.)7,7,9,9-Tetramethyl-2-octyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

16.)2-Decyl-7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

17.)2-Dodecyl-7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

18.){7,7,9,9-Tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]dec-2-yl}-methanol

19.) Acetic acid7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]dec-2-ylmethylester

20.) Octadecanoic acid7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]dec-2-ylmethylester

21.) Benzoic acid7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]dec-2-ylmethylester

22.)2-Methoxymethyl-7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

23.)2-Cyclohexyloxymethyl-7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

24.)2-Benzyloxymethyl-7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

25.) Octanedioic acidbis-{7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]dec-2-ylmethyl}ester

26.) Terephthalic acidbis-{7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]dec-2-ylmethyl}ester

27.)1′,4′-Bis-{7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]dec-2-ylmethyl}-oxybutane

28.)2,2,7,7,9,9-Hexamethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

29.)2,3,7,7,9,9-Hexamethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

30.)4,4-(o-Phenylendioxy)-2,2,6,6-tetramethyl-1-[1′-(4′-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

31.)4,4-(1′,2′-cyclohexylendioxy)-2,2,6,6-tetramethyl-1-[1″-(4″-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

32.)7,7,9,9-Tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane-2,3-dicarboxylicacid dimethyl ester

33.)8,8,10,10-Tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

34.)3,3,8,8,10,10-Hexamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

35.)3-Ethyl-3,8,8,10,10-pentamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

36.)3,3-Diethyl-8,8,10,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

37.)3,8,8,10,10-Pentamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-3-propyl-1,5-dioxa-9-aza-spiro[5.5]undecane

38.)3-Butyl-3-ethyl-8,8,10,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

39.)2,2,4,4-Tetramethyl-3-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-7,16-dioxa-3-aza-dispiro[5.2.5.2]hexadec-11-ene

40.){3,8,8,10,10-Pentamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undec-3-yl}-methanol

41.){3-Ethyl-8,8,10,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undec-3-yl}-methanol

42.)3-Methoxymethyl-3,8,8,10,10-pentamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

43.)3-Cyclohexyloxymethyl-3,8,8,10,10-pentamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

44.)3-Benzyloxymethyl-3,8,8,10,10-pentamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

45.) Acetic acid3,8,8,10,10-pentamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undec-3-ylmethylester

46.) Octanedioic acidbis-{3,8,8,10,10-pentamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undec-3-ylmethyl}ester

47.)1′,6′-Bis-{8,8,10,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undec-3-ylmethyl}-oxyhexane

48.)3,8,8,10,10-Pentamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane-3-carboxylicacid methyl ester

49.)8,8,10,10-Tetramethy-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane-3,3-dicarboxylicacid diethyl ester

50.)3,3-Bis-{8,8,10,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza}-spiro[5.5]undecane

51.)2,2,4,4-Tetramethyl-3-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-7,12-dioxa-3-aza-spiro[5.6]dodec-9-ene

Particularly preferred are the following compounds:4,4-Dibutoxy-2,6-diethyl-2,3,6-trimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

7,9-Diethyl-6,7,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

8,10-Diethyl-3,3,7,8,10-pentamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

{8,10-Diethyl-3,7,8,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undec-3-yl}-methanol

{3,8,10-Triethyl-7,8,10-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undec-3-yl}-methanol

4,4-Dibutoxy-2,2-diethyl-6,6-dimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

7,7-Diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

8,8-Diethyl-3,3,10,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

{8,8-Diethyl-3,10,10-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undec-3-yl}-methanol

{3,8,8-Triethyl-10,10-dimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undec-3-yl}-methanol

4,4-Dibutoxy-2,2,6,6-tetramethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

7,7,9,9-Tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

3,3,8,8,10,10-Hexamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

Most preferred is3,3,8,8,10,10-Hexamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

A further subject of the invention is a polymerizable composition,comprising a) at least one ethylenically unsaturated monomer oroligomer, and b) a compound of formula Ia, IIa, or IIIa

wherein

D is a group

or a group C(O)—R₁₃;

R₁₃ is phenyl or C₁–C₁₈alkyl;

m is 1, 2 or 3;

n is 1 or 2;

if n is 1

Y and Y′ are independently C₁–C₁₂alkyl, C₃–C₁₂alkenyl, C₃–C₁₂alkinyl,C₅–C₈cycloalkyl, phenyl, naphthyl, C₇–C₉phenylalkyl; or

Y and Y′ together form one of the bivalent groups —C(R₁)(R₂)—CH(R₃)—,CH(R₁)—CH₂—C(R₂)(R₃)—, —CH(R₂)—CH₂—C(R₁)(R₃)—, —CH₂—C(R₁)(R₂)—CH(R₃)—,o-phenylene, 1,2-cyclohexyliden,

—CH₂—CH═CH—CH₂— or

wherein

R₁ is hydrogen, C₁–C₁₂alkyl, COOH, COO—(C₁–C₁₂)alkyl or CH₂OR₄;

R₂ and R₃ are independently hydrogen, methyl ethyl, COOH orCOO—(C₁–C₁₂)alkyl;

R₄ is hydrogen, C₁–C₁₈alkyl, benzyl, or a monovalent acyl residuederived from an aliphatic, cycloaliphatic or aromatic monocarboxylicacid having up to 18 carbon atoms;

if n is 2

Y and Y′ together form one of the tetravalent groups

wherein

Q is a bisacyl residue which is derived from a C₂–C₁₂dicarboxylic acidor C₁–C₁₂alkylene;

Z is C₁–C₁₂alkylene;

the R₁₂ are independently of each other H or CH₃.

Definitions and preferences have already been given above for thecompounds. They apply also for the composition.

The monomers suitable for use in the present invention may bewater-soluble or water-insoluble. Water soluble monomers containtypically a salt of a carboxylic acid group. Water insoluble monomersare typically free of acid and phenolic groups. Typical metal atoms areNa, K or Li.

Typical monoethylenically unsaturated monomers free of carboxylic acidand phenolic groups which are suitable for this invention include thealkyl esters of acrylic or methacrylic acids such as methyl acrylate,ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate,butyl methacrylate and isobutyl methacrylate; the hydroxyalkyl esters ofacrylic or methacrylic acids, such as hydroxyethyl acrylate,hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropylmethacrylate; acrylamide, methacrylamid, N-tertiary butylacrylamide, N-mthylacrylamide, N,N-dimethylacrylamide; acrylonitrile,methacrylonitrile, allyl alcohol, dimethylaminoethyl acrylate,dimethylaminoethyl m thacrylat phosphoethyl methacrylate,N-vinylpyrrolidone, N-vinylformamide, N-vinylimidazole, vinyl acetate,conjugated dienes such as butadiene or isoprene, styrene,styrenesulfonic acid salts, vinylsulfonic acid salts and2-acrylamido-2-methylpropane-sulfonic acid salts and acryloil chloride.

Preferred ethylenically unsaturated monomers or oligomers are selectedfrom the group consisting of styrene, substituted styrene, conjugateddienes, acrolein, vinyl acetate, (alkyl)acrylic acidanhydrides,(alkyl)acrylic acid salts, (alkyl)acrylic esters or (alkyl)acrylamides.

Particularly preferred ethylenically unsaturated monomers are styrene,α-methyl styrene, p-methyl styrene, butadiene, methylacrylate,ethylacrylate, propylacrylate, n-butyl acrylate, tert.-butyl acrylateand acrylnitril.

In a most preferred composition the ethylenically unsaturated monomer isstyrene.

Preferred acrylates are methylacrylate, ethylacrylate, butylacrylate,isobutylacrylate, tert. butylacrylate, hydroxyethylacrylate,hydroxypropylacrylate, dimethylaminoethylacrylate, glycidylacrylates,methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate,hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate,dimethylaminoethyl(meth)acrylate, glycidyl(meth)acrylates,acrylonitrile, acrylamide or methacrylamide.

Examples for C₈–C₁₈ ethylenically unsaturated phenolics, which may alsobe used as comonomers include 4-hydroxy styrene, 4-hydroxy-α-methylstyrene, and 2,6-ditert. butyl, 4-vinyl phenol.

Another class of carboxylic acid monomers suitable for use as comonomersin this invention are the alkali metal and ammonium salts ofC₄–C₆-ethylenically unsaturated dicarboxylic acids. Suitable examplesinclude maleic acid, maleic anhydride, itaconic acid, mesaconic acid,fumaric acid and citraconic acid. Maleic anhydride (and itaconic acidare) is the preferred monoethylenically unsaturated dicarboxylic acidmonomer(s).

The acid monomers suitable for use in this invention are in the form ofthe alkali metal salts or ammonium salts of the acid.

The polymerizable composition of the present invention may additionallycomprise a solvent selected from the group consisting of water,alcohols, esters, ethers, ketones, amides, sulfoxides, hydrocarbons andhalogenated hydrocarbons.

The invention also relates to a free radical polymerization process andpolymers obtained thereby, which process overcomes many of the problemsand disadvantages of the afore mentioned prior art processes.

Preferably the initiator compound is present in an amount of from 0.01mol-% to 20 mol-%, more preferably in an amount of from 0.01 mol-% to 10mol-% and most preferred in an amount of from 0.05 mol-% to 10 mol-%based on the monomer or monomer mixture.

When monomer mixtures are used mol-% is calculated on the averagemolecular weight of the mixture.

Another subject of the present invention is a process for preparing anoligomer, a cooligomer, a polymer or a copolymer (block or random) byfree radical polymerization of at least one ethylenically unsaturatedmonomer or oligomer, which comprises (co)polymerizing the monomer ormonomers/oligomers in the presence of an initiator compound of formulaIa, IIa or IIIa under reaction conditions capable of effecting scissionof the O—C bond to form two free radicals, the radical

being capable of initiating polymerization.

Preferably the scission of the O—C bond is effected by heating and takesplace at a temperature of between 50° C. and 160° C.

Preferred initiators and ethylenically unsaturated monomers have alreadybeen mentioned above.

Polydispersity (PD) of the polymers prepared by the present invention ispreferably between 1.0 and 2.0, more preferably between 1.1 and 1.8 andand most preferably between 1.1 and 1.6.

The process may be carried out in the presence of an organic solvent orin the presence of water or in mixtures of organic solvents and water.Additional cosolvents or surfactants, such as glycols or ammonium saltsof fatty acids, may be present. Other suitable cosolvents are describedhereinafter.

Preferred processes use as little solvents as possible. In the reactionmixture it is preferred to use more than 30% by weight of monomer andinitiator, particularly preferably more than 50% and most preferrablymore than 80%.

If organic solvents are used, suitable solvents or mixtures of solventsare typically pure alkanes (hexane, heptane, octane, isooctane),hydrocarbons (benzene, toluene, xylene), halogenated hydrocarbons(chlorobenzene), alkanols (methanol, ethanol, ethylene glycol, ethyleneglycol monomethyl ether), esters (ethyl acetate, propyl, butyl or hexylacetate) and ethers (diethyl ether, dibutyl ether, ethylene glycoldimethyl ether), or mixtures thereof.

The aqueous polymerization reactions can be supplemented with awater-miscible or hydrophilic cosolvent to help ensure that the reactionmixture remains a homogeneous single phase throughout the monomerconversion. Any water-soluble or water-miscible cosolvent may be used,as long as the aqueous solvent medium is effective in providing asolvent system which prevents precipitation or phase separation of thereactants or polymer products until after all polymerization reactionshave been completed. Exemplary cosolvents useful in the presentinvention may be selected from the group consisting of aliphaticalcohols, glycols, ethers, glycol ethers, pyrrolidines, N-alkylpyrrolidinones, N-alkyl pyrrolidones, polyethylene glycols,polypropylene glycols, amides, carboxylic acids and salts thereof,esters, organosulfides, sulfoxides, sulfones, alcohol derivatives,hydroxyether derivatives such as butyl carbitol or cellosolve, aminoalcohols, ketones, and the like, as well as derivatives thereof andmixtures thereof. Specific examples include methanol, ethanol, propanol,dioxane, ethylene glycol, propylene glycol, diethylene glycol, glycerol,dipropylene glycol, tetrahydrofuran, and other water-soluble orwater-miscible materials, and mixtures thereof. When mixtures of waterand water-soluble or water-miscible organic liquids are selected as theaqueous reaction media, the water to cosolvent weight ratio is typicallyin the range of about 100:0 to about 10:90.

When monomer mixtures or monomer/oligomer mixtures are used, thecalculation of mol-% is based on an average molecular weight of themixture.

Hydrophilic monomers, polymers and copolymers of the present inventioncan be separated from one another or from the polymerization reactionmixture by, for example, changing the pH of the reaction media and byother well known conventional separation techniques.

The polymerization temperature may range from about 50° C. to about 180°C., preferably from about 80° C. to about 150° C. At temperatures aboveabout 180° C., the controlled conversion of the monomer into polymerdecreases, and uncertain and undesirable by-products like thermallyinitiated polymer are formed or destruction of the polymerizationregulator may occur. Frequently, these by-products discolor the polymermixture and a purification step may be required to remove them, or theymay be intractable.

Therefore high reactivity of the present initiators which are alreadyactive at relatively low temperatures leads to short reaction times. Theresulting polymers are usually colourless and they can be used in mostcases without any further purification step. This is an importantadvantage when industrial scale-up is considered.

After the polymerizing step is complete, the formed (co)polymer obtainedis isolated. The isolating step of the present process is conducted byknown procedures, e.g. by distilling off the unreacted monomer or byprecipitation in a suitable nonsolvent, filtering the precipitatedpolymer followed by washing and drying the polymer.

Furthermore, block copolymers of this invention, wherein the blocksalternate between polar monomers and non-polar monomers, are useful inmany applications as amphiphilic surfactants or dispersants forpreparing highly uniform polymer blends.

The (co)polymers of the present invention may have a number averagemolecular weight from 1 000 to 400 000 g/mol, preferably from 2 000 to250 000 g/mol and, more preferably, from 2 000 to 200 000 g/mol. Whenproduced in bulk, the number average molecular weight may be up to 500000 (with the same minimum weights as mentioned above). The numberaverage molecular weight may be determined by size exclusionchromatography (SEC), gel permeation chromatography (GPC), matrixassisted laser desorption/ionization mass spectrometry (MALDI-MS) or, ifthe initiator carries a group which can be easily distinguished from themonomer(s), by NMR spectroscopy or other conventional methods.

Thus, the present invention also encompasses in the synthesis novelblock, multi-block, star, gradient, random, hyperbranch d and dendriticcopolymers, as well as graft or copolymers.

The polymers prepared by the present invention are useful for example infollowing applications:

adhesives, detergents, dispersants, emulsifiers, surfactants, defoamers,adhesion promoters, corrosion inhibitors, viscosity improvers,lubricants, rheology modifiers, impact modifiers, thickeners,crosslinkers, paper treatment, water treatment, electronic materials,paints, coatings, photography, ink materials, imaging materials,superabsorbants, cosmetics, hair products, preservatives, biocidematerials or modifiers for asphalt, leather, textiles, ceramics andwood.

Because the present polymerizaton is a “living” polymerization, it canbe started and stopped practically at will. Furthermore, the polymerproduct retains the functional alkoxyamine group allowing a continuationof the polymerization in a living matter. Thus, in one embodiment ofthis invention, once the first monomer is consumed in the initialpolymerizing step a second monomer can then be added to form a secondblock on the growing polymer chain in a second polymerization step.Therefore it is possible to carry out additional polymerizations withthe same or different monomer(s) to prepare multi-block copolymers.Furthermore, since this is a radical polymerization, blocks can beprepared in essentially any order. One is not necessarily restricted topreparing block copolymers where the sequential polymerizing steps mustflow from the least stabilized polymer intermediate to the moststabilized polymer intermediate, such as is the case in ionicpolymerization. Thus it is possible to prepare a multi-block copolymerin which a polyacrylonitrile or a poly(meth)acrylate block is preparedfirst, then a styrene or butadiene block is attached thereto, and so on.

Furthermore, there is no linking group required for joining thedifferent blocks of the present block copolymer. One can simply addsuccessive monomers to form successive blocks.

A plurality of specifically designed polymers and copolymers areaccessible by the present invention, such as star and graft (co)polymersas described, inter alia, by C. J. Hawker in Angew. Chemie, 1995, 107,pages 1623–1627, dendrimers as described by K. Matyaszewski et al. inMacromol cules 1996, Vol 29, No.12, pages 4167–4171, graft (co)polymersas described by C. J. Hawker et al. in Macromol. Chem. Phys. 198,155–166(1997), random copolymers as described by C. J. Hawker inMacromolecules 1996, 29, 2686–2688, or diblock and triblock copolymersas described by N. A. Listigovers in Macromolecules 1996, 29, 8992–8993.

Still further subjects of the invention are a polymer or oligomer,containing at least one initiator group

and at least one oxyamine group of formula Ib, IIb or IIIb

wherein Y and Y′ are as defined above, obtainable by the processdescribed above; and the use of a compound of formula Ia, IIa or IIIafor polymerizing ethylenically unsaturated monomers.

Also subject of the invention is the use of a compound of formula Ia,IIa or IIIa for terminating the anionic polymerization of a diene orvinyl monomer.

When the compounds are used for such termination reactions they areusually used in an equimolar amount or in excess to the initiating base,such as for example sec. butyl-litium.

The preparation of the compounds of the present invention is carried outaccording to known reaction steps. A general method for the preparationof the compounds of formula Ia, IIa, and IIIa starts from the 4-oxocompounds Xa or XIa which are described in GB 2335190 or from XIIa whichis a known compound described for example in DE 2352127.

These starting compounds are reacted for example with suitablemonoalcohols, diols or tetrafunctional alcohols to form intermediates offormula Xb, XIb or XIIb wherein Y, Y′ and n are as defined above. Suchketalization reactions are well known in the art and the correspondingcompounds are mostly known. The reaction is for example described inU.S. Pat. Nos. 3,790,525, 3,899,464, 4,007,158 and 4,105,626.

The compounds of formula Xb, XIb and XIIb are oxidized according tostandard procedures to the corresponding nitroxides of formula Xc, XIcand XIIc, as for example described in GB 2335190 or WO 99/46261.

The nitroxides are then reacted with a compound of formula

wherein R₁₂ and m are as defined above to obtain a compound of formulaIa, IIa or IIIa.

This coupling reaction is also descriebed for example in GB 2335190 orin WO 99/46261. Preferably the coupling reaction is carried out in thepresence of a Cu(II) salt according to the method described inInternational Application No. PCT/EP01/05668.

Alternatively the nitroxides of formula Xc, XIc or XIIc can be reactedwith a compound of formula

The reaction products are subsequently hydrolyzed to form a compound offormula Xd, XId or XIId.

These compounds are novel and consequently are also subject of thepresent invention. The above given definitions and preferences applyalso for the compounds of formula Xd, XId and XIId.

The compounds of formula Xd, XId and XIId can be reacted withepichlorohydrine and compounds according to formula Ia, IIa or IIIa areobtained.

The following examples illustrate the invention.

Preparation of an Intermediate According to Formula XIId.

Preparation of Acetic Acid4-[1-(3,3,8,8,10,10-hexamethyl-1,5-dioxa-9-aza-spiro[5.5]undec-9-yloxy)-ethyl]-phenylEster

A mixture of 25.6 g3,3,8,8,10,10-hexamethyl-1,5-dioxa-9-aza-spiro[5.5]undecan-9-oxyl(prepared according to EP 574666A1) and 82.1 g acetic acid4-ethyl-phenyl ester are heated to 50° C. with stirring and 0.68 ml ofan ethanolic solution containing 0.13 g copper(II)chloride is added. Thetemperature is raised to 65° C. and 19.4 g of an aqueous solution ofbutylhydroperoxide in water (70%) are dropwise added. The reactionmixture is allowed to further react for 22 h at 65°–70° C. andsubsequently cooled to room temperature. Excess tert.-butylhydroperoxideis removed by dropwise adding 4 ml of an aqueous sodium pyrosulfitesolution (20%). To the reaction mixture 50 ml acetic acid ethylester areadded and the organic and aqueous phase are separated. The organic phaseis washed with a saturated NaCl solution. After drying with sodiumsulfate and evaporation of the solvent an oil is obtained, from whichexcess acetic acid 4-ethyl-phenyl ester is removed by distillation (100°C./0.025 mbar). The residue is dissolved in methanol/hexane (4/1 byvolume) on heating to refux. After cooling to 0° C. the precipitate isfiltered off. After recrystalization from acetone white crystals areobtained having a melting point of 124–125° C.

Preparation of4-[1-(3,3,8,8,10,10-Hexamethyl-1,5-dioxa-9-aza-spiro[5.5]undec-9-yloxy)-ethyl]-phenol

A mixture of 8 g acetic acid4-[1-(3,3,8,8,10,10-hexamethyl-1,5-dioxa-9-aza-spiro[5.5]undec-9-yloxy)-ethyl]-phenylester and 3.9 g potassium carbonate in 60 ml methanol is stirred for onehour at room temperature. The mixture is cooled to 0° C. and neutralizedby adding 60 ml of 0.5 M hydrochloric acid. The white suspension isdiluted with water (60 ml) and filtered through a buchner funnel. Theresidue is washed with water and dried in a vacuum oven at 50° C. Awhite solid having a melting point of 133–134° C. is obtained.

Preparation of Compounds According to Formulae Ia, IIa and IIIa

EXAMPLE A1 Preparation of7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decan

A mixture of 50 g7,7,9,9-tetramethyl-1,4-dioxa-8-aza-spiro[4.5]decan-8-oxyl (preparedaccording to EP 574666A1) and 124.75 g 2-(4-ethyl-phenoxymethyl)-oxiranare heated to 60° C. with stirring and a solution of 0.32 gcopper(II)chloride in 1.6 ml ethanol is added. 45 g of an aqueoussolution of butylhydroperoxide in water (70%) is dropwise added. Thereaction mixture is allowed to further react for 16 h at 60° C. andsubsequently cooled to room temperature. Excess tert.-butylhydroperoxideis removed by dropwise adding 15 ml of an aqueous sodium pyrosulfitesolution. To the reaction mixture 100 ml acetic acid ethylester areadded and the organic and aqueous phase are separated. The organic phaseis washed twice with 200 ml of a saturated NaCl solution. After dryingwith sodium sulfate and evaporation of the solvent an oil is obtained,from which excess 2-(4-ethyl-phenoxymethyl)-oxiran is removed bydistillation (100° C./0.005 mbar). The residue is dissolved in hexanefiltered over aluminium oxide and the solvent is again evaporated. Afterrecrystalization from hexane white crystals are obtained having amelting point of 73.5–74.2° C.

EXAMPLE A2 Preparation of3,3,8,8,10,10-hexamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecan

The title compound is prepared in analogy to example A1 from3,3,8,8,10,10-hexamethyl-1,5-dioxa-9-aza-spiro[5.5]undecan-9-oxyl(prepared according to EP 574666A1). White crystals are obtained.

Elemental analysis: calculated: 69.25% C; 9.07% H; 3.23% N; found:68.86% C; 9.05% H; 3.18% N.

The following compounds are prepared according to example A1, startingfrom the corresponding nitroxide.

Phys. No. Struktur Daten NMR Data A3

¹H-NMR(400MHz; δ in ppm; CDCl₃):0.63(broad s, 3H); 1.0–1.95(m,16H);1.45–1.47(d, 3H); 2.73–2.75(m, 1H); 2.88–2.9(m, 1H); 3.2–3.55(m,2H);3.85–4.3(m, 4H); 4.72–4.77(q, 1H);6.84–6.87 and 7.22–7.25(aromaticH,4H). A4

m.p.52–58.5° C. A5

m.p.118.5–121° C. A6

m.p.88.5–93° C. A7

m.p.64.5–67° C. A8

m.p.102–109° C. A9

m.p.56–59° C. A10

¹H-NMR(400MHz; δ in ppm; CDCl₃):0.55–1.65(m, 31H); 1.95–2.25(m,2H);2.74–2.76(m, 1H); 2.89–2.91(m,1H); 3.35(m, 1H); 3.5(m, 4H);3.94–3.98(m, 1H); 4.17–4.21(m, 1H); 4.71–4.76(q, 1H); 6.84–6.87 and7.22–7.25(aromatic H, 4H). A11

m.p.119.5–128° C. A12

m.p.116–121.5° C. A13

m.p.66.5–68.5° C. A14

m.p.42–55° C. A15

¹H-NMR(400MHz; δ in ppm; CDCl₃):0.55–2.4(m, 39H); 2.74–2.76(m, 1H);2.88–2.91(m, 1H);3.3–3.7(m, 9H); 3.94–3.98(m, 1H);4.17–4.21(m, 1H);4.71–4.76(q,1H); 6.84–6.87 and 7.22–7.25(aromatic H, 4H). A16

m.p.82–88° C. ¹H-NMR(400MHz; δ in ppm; CDCl₃):0.6–1.65(m, 23H);2–2.25(m, 2H);2.75–2.78(m, 1H); 2.89–2.91(m, 1H);3.3–3.4(m, 1H); 3.45(s,4H);3.9–4.0(m, 1H); 4.15–4.25(m,1H); 4.7–4.77(q, 1H);6.75–7.25(aromaticH, 4H). A17

¹H-NMR(300MHz; δ in ppm; CDCl₃):0.7–1.7(m, 17H); 0.95(s, 6H);2–2.25(m,2H); 2.74–2.79(m, 1H); 2.87–2.9(m, 1H); 3.3–3.4(m, 1H); 3.46(s, 4H);3.9–4.05(m, 1H); 4.15–4.25(m, IH); 5.2–5.3(q, 1H); 6.8–7.5(aromatic H,4H).

EXAMPLE A18{4-[1-(3,3,8,8,10,10-Hexamethyl-1,5-dioxa-9-aza-spiro[5.5]undec-9-yloxy)-ethyl]-phenyl}-phenyl-methanone

A mixture of 50 g3,3,8,8,10,10-hexamethyl-1,5-dioxa-9-aza-spiro[5.5]undecan-9-oxyl (CAS98254-32-1) and 41 g (4-Ethyl-phenyl)-phenyl-methanone (preparation byFriedel-Crafts acylation of 4-ethylbenzene with benzoylchloride) isheated to 60° C. and a solution of 0.26 g copper(II)chloride in 1.3 mlethanol is added. 53.7 g of a 70% aqueous solution oftert-butylhydroperoxide in water are added dropwise. The reactionmixture is allowed to further react for 28 h and subsequently cooled toroom temperature. Excess tert-butylhydroperoxide is then removed bydropwise adding an aqueous solution of sodium pyrosulfite. To thereaction mixture 100 ml of ethyl acetate are added and the organic phaseis separated from the aqueous phase. The organic phase is washed twicewith water (200 ml) and the solvent evaporated. The residue is purifiedchromatographically on silica gel with hexane/ethyl acetate (7:3 byvolume) as the eluente. After recrystallization from pentane/ethanol(5:3 by volume) white crystals of a compound of formula

are obtained having a melting range of 104–117° C.

¹H-NMR (300 MHz; δ in ppm; CDCl₃): 0.7 (s broad, 3H); 0.94 (s broad,6H); 1.18 (s broad, 3H); 1.33 (s broad, 6H); 1.51–1.53 (d, 3H); 1.4–1.65(m, 2H); 2–2.25 (m, 2H); 3.46 (s broad, 4H); 4.84–4.91 (q, 1H); 7.4–7.9(aromatic H, 9H).

EXAMPLE A198,8-Diethyl-3,3,10,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

To a stirred mixture of 25.6 g8,8-diethyl-3,3,10,10-tetramethyl-1,5-dioxa-9-aza-spiro[5.5]undecan-9-oxyland 80.2 g 2-(4-ethyl-phenoxymethyl)-oxirane at 50° C. is added asolution of 0.12 g copper(II)chloride in 0.6 ml ethanol. The temperatureof the reaction mixture is increased to 70° C. and 11.6 g of a 70%aqueous solution of tert-butylhydroperoxide in water are added dropwise.The reaction mixture is allowed to further react for 6 h at 70° C. andsubsequently cooled to room temperature. Excess tert-butylhydroperoxideis removed by dropwise adding an aqueous solution of sodium pyrosulfite(2 ml). To the reaction mixture 50 ml of ethyl acetate and 50 ml 10%aqueous solution of sodium chloride are added. The mixture is filteredthrough celite and the organic phase is separated. The organic phase iswashed three times with 10% aqueous solution of sodium chloride (100 ml)and dried over sodium sulfate. After evaporation of the solvent an oilis obtained, from which excess 2-(4-ethyl-phenoxymethyl)-oxirane isremoved by distillation (80° C., 0.025 mbar). A highly viscous residueis obtained which crystallises on standing at room temperature. Afterrecrystallization twice from methanol whit crystals of the compound offormula

are obtained having a melting point of 82–85° C.

According to the preparation of8,8-Diethyl-3,3,10,10-tetramethyl-9-[1-(4-oxiranylmethoxyphenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane,the following compounds are synthesized in analogy:

No. Structure NMR-data A20

¹H-NMR(400MHz; δ in ppm;CDCl₃): 0.4–2.5(m, 27H);2.75–2.76(m, 1H);2.89–2.91(m, 1H); 3.34–3.36(m, 1H);3.4–3.55(m, 2H); 3.7–3.85(m,2H);3.94–3.98(m, 1H); 4.18–4.21(m, 1H); 4.63–4.68(q, 1H);6.84–6.86 and7.19–7.21(aromatic H, 4H). A21

¹H-NMR(400MHz; δ in ppm;CDCl₃): 0.5–2.2(m, 23H);2.74–2.76(m, 1H);2.89–2.91(m, 1H); 3.33–3.37(m, 1H);3.7–4.05(m, 5H); 4.18–4.21(m,1H);4.64–4.69(q, 1H); 6.84–6.87 and 7.19–7.21(aromatic H, 4H).

EXAMPLE A228,10-diethyl-3,3,7,8,10-pentamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxyl]-1,5-dioxa-9-aza-spiro[5,5]undecane

To a stirred mixture of 59.7 g8,10-diethyl-3,3,7,8,10-pentamethyl-1,5-dioxa-9-aza-spiro[5.5]undecan-9-oxyland 178.2 g 2-(4-ethyl-phenoxymethyl)-oxirane a solution of 0.27 gcopper(II)chloride in 1.35 ml ethanol is added at about 60° C. Then 38.7g of a 70% aqueous solution of tert-butylhydroperoxide in water areadded dropwise. An exothermic reaction started and the temperature iskept at 70° C. The reaction mixture is allowed to further react for 24 hat 70° C. and subsequently cooled to room temperature. The reactionmixture is diluted with 100 ml of ethyl acetate. Excesstert-butylhydroperoxide is removed by dropwise adding an aqueoussolution of sodium pyrosulfite (70 ml) below 20° C. The organic phase isseparated, washed twice with 10% aqueous solution of sodium chloride(100 ml) and dried over sodium sulfate. After evaporation of the solventan oil is obtained, from which excess 2-(4-ethyl-phenoxymethyl)-oxiraneis removed by distillation (80° C., 0.025 mbar). A highly viscous resinis obtained which is dissolved in methanol (20 ml) and cooled to about−18° C. White crystals precipitate and are collected by filtrationhaving a melting point of 141–147° C. The compound has the followingstructural formula

According to the preparation of8,10-Diethyl-3,3,7,8,10-pentamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane,the following compound is synthesized in analogy:

No. Structure A23

¹H-NMR(400MHz; δ in ppm;CDCl₃): 0.5–2.3(m, 25H);2.75–2.76(m, 1H);2.89–2.91(m, 1H); 3.34–3.36(m,1H); 3.7–4.1(m, 5H); 4.18–4.21(m, 1H);4.66–4.72(m, 1H);6.83–6.86 and 7.18–7.21(aromatic H, 4H).Polymerization Experiments with Styrene

EXAMPLE B1

Styrene is distilled under reduced pressure prior to use. In a dry,argon-purged Schlenk tube, the amounts of nitroxyl ether given in Table1 are dissolved in 50 ml styrene. The solution is degauss d in threeconsecutive freeze-thaw-cycles and then purged with argon. The stirredsolution is then immersed in an oil bath and polymerized at the giventemperature for 6 hours. After polymerization, residual monomer isremoved under vacuum at 60° C. and the polymer is dried at 60° C. invacuo until constant weight is achieved. Molecular weight and molecularweight distributions are determined by size exclusion chromatography(SEC) on a HP 1090 liquid chromatograph (software: winGPC/PolymerStandard Services, Mainz, Germany) using THF as eluent and a columncombination calibrated with narrow polystyrene standards (PolymerLaboratories). The results are given in Table 1.

NOR of example A2

TABLE 1 Styrene Temp. mol % Conversion M_(n) M_(n) M_(w) M_(w)/M_(n) NOR[° C.] NOR (%) (calc.) (GPC) (GPC) (GPC) Example A2 120   1 mol % 404700 4300 5200 1.24 Example A2 120 0.1 mol % 44 46000 28400 36900 1.30Example A2 130   1 mol % 48 5300 4800 5800 1.21 Example A2 130 0.1 mol %61 64500 37200 49500 1.33

Following the general description of example B1 further polymerizationsin styrene were carried out and the following results obtained.

EXAMPLE B2

NOR of example A1

TABLE 2 Temp. Mol % Yield M_(n) Exp. # (° C.) NOR (%) (calc.) M_(n)M_(w) M_(w)/M_(n) 1 120 1 20 2400 1800 2200 1.25 2 120 0.1 41 4340023300 37000 1.59 3 130 1 41 4700 3500 4300 1.23 4 130 0.1 55 58000 3090042900 1.39

EXAMPLE B3

NOR of example A6

TABLE 3 Temp. Mol % Yield M_(n) Exp. # (° C.) NOR (%) (calc.) M_(n)M_(w) M_(w)/M_(n) 1 120 1 41 4600 3700 4500 1.22 2 120 0.1 46 4790032500 41000 1.26 3 130 1 46 5200 3900 4700 1.18 4 130 0.1 61 63800 3860050200 1.30

EXAMPLE B4

NOR of example A5

TABLE 4 Temp. Mol % Yield M_(n) Exp. # (° C.) NOR (%) (calc.) M_(n)M_(w) M_(w)/M_(n) 1 120 1 39 4500 3500 4300 1.21 2 120 0.1 51 5350034800 42700 1.23 3 130 1 52 5800 4400 5500 1.24 4 130 0.1 59 61800 3140044200 1.41

EXAMPLE B5

NOR of example A4

TABLE 5 Temp. Mol % Yield M_(n) Exp. # (° C.) NOR (%) (calc.) M_(n)M_(w) M_(w)/M_(n) 1 120 1 26 3100 2600 3200 1.23 2 120 0.1 37 3900027700 35400 1.28 3 130 1 51 5700 4800 6000 1.24 4 130 0.1 57 59600 3540047800 1.35

EXAMPLE B6

NOR of example A9

TABLE 6 Temp. Mol % Yield M_(n) Exp. # (° C.) NOR (%) (calc.) M_(n)M_(w) M_(w)/M_(n) 1 120 1 26 3100 2700 3300 1.26 2 120 0.1 38 4040028100 35700 1.27 3 130 1 54 6100 5000 6000 1.20 4 130 0.1 60 62600 3760049500 1.32Polymerization with n-BuA

EXAMPLE B7

n-Butylacrylate is destined under reduced pressure prior to use. In adry, argon-purged Shlenk tube, the amounts of nitroxyl ether given inTable A are dissolved in 62.5 ml n-butylacrylate. The solution isdegassed in three consecutive freez-thaw-cycles and then purged withargon. The stirred solution is then immersed in an oil bath andpolymerized at 130° C. for 6 hours. After polymerization, residualmonomer is removed under vacuum at 30° C. and the polymer is dried at30° C. in vacuum until constant weight is achieved.

Molecular weight and molecular weight distributions are determined bysize exclusion chromatography (SEC) on a HP 1090 liquid chromatograph(software: winGPC/Polymer Standard Services, Mainz, Germany) using THFas eluent and a column combination calibrated with narrow polystyrenestandards (Polymer Laboratories). The results are given in Table 7.

TABLE 7 Temp. mol % n-BuA Mn Mw Mw/Mn NOR of [° C.] NOR Conv. [%] Mn(calc.) (GPC) (GPC) (GPC) example A20 130   1 mol % 45 6217 6761 80951.20 example A20 130 0.1 mol % 41 52856 45900 56710 1.24 example A19 130  1 mol % 54 7373 7046 8574 1.22 example A19 130 0.1 mol % 35 4573139070 47090 1.21 example A22 130   1 mol % 61 8233 8137 9762 1.20example A22 130 0.1 mol % 60 77326 57120 72870 1.28

EXAMPLE B8 Anionic Polymerization and Termination of Isoprene with theCompound of Example A2

To 10.2 g (0.15 mol) isoprene dissolved in 50 ml dry toluene in a driedampule with teflon valve equipped with a magnetic stir bar are added ina dry argon atmosphere 3.34×10⁻³ mol sec.-butyllithium (1.3 mol/Lsolution in cyclohexane, Fluka) and stirred for 18 hours at roomtemperature to allow polymerization. Subsequently a sample of theresulting prepolymer is drawn via syringe, dried at room temperature invacuo and submitted to GPC. To the residual, slightly yellowpolyisoprene solution is slowly added a calculated amount of thecompound of example A2 (1.2 and 1.5 fold molar excess with respect tothe initial molar amount of sec.-butyllithium used) (dissolved intoluene and degassed) via syringe. The mixture is allowed to react foranother 6 hours at room temperature. Subsequently the terminationreaction is quenched adding a few ml of degassed methanol. Volatiles areremoved in vacuo and the resulting polyisoprene is obtain d as a slightyellow rubber after drying at room temperature in vacuo until constantweight is achieved. Molecular weights are determined by GPC on a HP 1090equipped with a RI and DAAD (set at 254 nm) detector with THF as eluent(1 ml/min), using PS standards for calibration.

M_(n)(GPC) (RI terminating conversion detection) M_(w)/M_(n) agent ofisoprene M_(n) (calc.) prepolymer/polymer prepolymer/polymer Ex. exampleA2 (%) (prepolymer) after reaction after reaction 1 1.2 × excess 93 28002700* 3500** 1.23* 1.16** 2 1.5 × excess 81 2400 2600* 3300** 1.20*1.14** *polymer before termination with the compound of example A2**polymer after termination with the compound of example A2Reinitiation of Terminated Polyisoprene with Styrene (Terminating Agentis Compound of Example A2)

In a dried, argon purged Schlenk tube equipped with an argon inlet and amagnetic stir bar, 5 g of samples 1 and 2 above are dissolved in 25 g offreshly distilled styrene each. The solutions are degassed by twoconsecutive freeze-thaw cycles and immersed in an oil bath at 120° C. toallow polymerization. After 6 hours, residual monomer is removed invacuo and the resulting polymer is dried in vacuo at 70° C. untilconstant weight is achieved. Molecular weights are determined asdescribed before.

macroinitator conversion M_(n) M_(n) M_(w)/ example used styrene (%)(initial) (blockcopolymer) M_(n) 3 1 24 3500 5900 1.27 4 2 24 3300 44001.34

1. A polymerizable composition, comprising a) at least one ethylenicallyunsaturated monomer or oligomer, and b) a compound of formula Ia, IIa orIIIa

wherein D is a group

or a group C(O)—R₁₃; R₁₃ is phenyl or C₁–C₁₈alkyl; m is 1, 2 or 3; n is1 or 2; if n is 1 Y and Y′ together form one of the bivalent groups—C(R₁)(R₂)—CH(R₃)—, CH(R₁)—CH₂—C(R₂)(R₃)—, —CH(R₂)—CH₂—C(R₁)(R₃)—,—CH₂—C(R₁)(R₂)—CH(R₃)—, o-phenylene, 1,2-cyclohexyliden, —CH₂—CH═CH—CH₂—or

wherein R₁ is hydrogen, C₁–C₁₂alkyl, COOH, COO—(C₁–C₁₂)alkyl or CH₂OR₄;R₂ and R₃ are independently hydrogen, methyl ethyl, COOH orCOO—(C₁–C₁₂)alkyl; R₄ is hydrogen, C₁–C₁₂alkyl, benzyl, or a monovalentacyl residue of an aliphatic, cycloaliphatic or aromatic monocarboxylicacid having up to 18 carbon atoms; if n is 2 Y and Y′ together form oneof the tetravalent groups

wherein Q is a bisacyl residue of a C₂–C₁₂dicarboxylic acid orC₁–C₁₂alkylene; Z is C₁–C₁₂alkylene; the R₁₂ are independently of eachother H or CH₃.
 2. A polymerizable composition according to claim 1,wherein the ethylenically unsaturated monomers or oligomers are selectedfrom the group consisting of styrene, substituted styrene, conjugateddienes, acrolein, vinyl acetate, (alkyl)acrylic acidanhydrides,(alkyl)acrylic acid salts, (alkyl)acrylic esters and (alkyl)acrylamides.3. A polymerizable composition according to claim 2, wherein theethylenically unsaturated monomers are styrene, α-methyl styrene,p-methyl styrene, butadiene, methylacrylate, ethylacrylate,propylacrylate, n-butyl acrylate, tert-butyl acrylate or acrylnitril. 4.A polymerizable composition according to claim 1, wherein the compoundof formula Ia, IIa or IIIa is present in an amount of from 0.01 mol-% to20 mol-% based on the monomer.
 5. A process for preparing an oligomer, acooligomer, a polymer or a copolymer (block or random) by free radicalpolymerization of at least one ethylenically unsaturated monomer oroligomer, which comprises (co)polymerizing the at least one monomer oroligomer in the presence of an initiator compound of formula Ia, IIa orIIIa under reaction conditions capable of effecting scission of the O—Cbond to form two free radicals, the radical

being capable of initiating polymerization, where the compounds offormula Ia, IIa or IIIa are

wherein D is a group

or a group C(O)—R₁₃; R₁₃ is phenyl or C₁–C₁₈alkyl; m is 1,2 or 3; n is 1or 2; if n is 1 Y and Y′ together form one of the bivalent groups—C(R₁)(R₂)—CH(R₃)—, CH(R₁)—CH₂—C(R₂)(R₃)—, —CH(R₂)—CH₂—C(R₁)(R₃)—,—CH₂—C(R₁)(R₂)—CH(R₃)—, o-phenylene, 1,2-cyclohexyliden, —CH₂—CH═CH—CH₂—or

wherein R₁ is hydrogen, C₁–C₁₂alkyl, COOH, COO—(C₁—C₁₂)alkyl or CH₂OR₄;R₂ and R₃ are independently hydrogen, methyl ethyl, COOH orCOO—(C₁–C₁₂)alkyl; R₄ is hydrogen, C₁–C₁₂alkyl, benzyl, or a monovalentacyl residue of an aliphatic, cycloaliphatic or aromatic monocarboxylicacid having up to 18 carbon atoms; if n is 2 Y and Y′ together form oneof the tetravalent groups

wherein Q is a bisacyl residue of a C₂–C₁₂dicarboxylic acid orC₁–C₁₂alkylene; Z is C₁–C₁₂alkylene; the R₁₂ are independently of eachother H or CH₃.
 6. A process according to claim 5, wherein the scissionof the O—C bond is effected by heating and takes place at a temperatureof between 50° C. and 160° C.
 7. A polymerizable composition accordingto claim 1 where the compounds of formula Ia, IIa or IIIa are7,9-Diethyl-6,7,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane;8,10-Diethyl-3,3,7,8,10-pentamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane;{8,10-Diethyl-3,7,8,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undec-3-yl}-methanol;{3,8,10-Triethyl-7,8,10-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undec-3-yl}-methanol;7,7-Diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane;8,8-Diethyl-3,3,10,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane;{8,8-Diethyl-3,10,10-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undec-3-yl}-methanol;{3,8,8-Triethyl-10,10-dimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undec-3-yl}-methanol;7,7,9,9-Tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane;or3,3,8,8,10,10-Hexamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane.